Polyamide compounds, molds produced therefrom and use of the polyamide compounds
The present invention relates to polyamide compounds having high heat aging resistance which, in addition to a specific polyamide, comprise at least one unsubstituted or substituted metallocene, optionally at least one impact modifier and optionally at least one additive. The invention also relates to the use of said polyamide compounds for the production of molds.
1. A polyamide compound comprising:
(A) 32 to 89.6 wt. % of at least one partially crystalline, partially aromatic polyamide,
(B) 10 to 30 wt. % of at least one impact modifier,
which is (i) a copolymer of a monomer selected from the group consisting of ethylene, propylene, an acrylate monomer, acrylic acid, vinyl acetate, and styrene with a monomer selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic acid derivative, and an unsaturated glycidyl compound,
or which is (ii) a functionalized polymer formed by grafting a polymer selected from the group consisting of polyethylene, polypropylene, a polyolefin copolymer, an acrylate copolymer, an acrylic acid copolymer, a vinyl acetate copolymer, a styrene copolymer, ionic ethylene copolymer in which the acid group or acid groups are partially neutralized with metal ions, and a core-shell impact modifier, with a compound selected from the group consisting of an unsaturated carboxylic acid, unsaturated carboxylic acid derivative, and unsaturated glycidyl compound,
(C) 0.01 to 3.0 wt. % of at least one substituted or unsubstituted metallocene, wherein the unsubstituted metallocene is not ferrocene, and
wherein a substituent of the at least one substituted metallocene is selected from the group consisting of alkyl, alkylene, arylene moieties, carboxylic acid moieties, moieties of carboxylic acid derivatives, oxoalkanoic acids, alcohols, amines, and moieties of phosphorus-containing substituents, or wherein the at least one substituted metallocene is selected from the group consisting of 3-carboxybutyrylferrocene, 3-carboxypropionylferrocene, 6-mercaptohexylferrocene, aminomethylferrocenes, dimethylaminomethylferrocene, diphenylphosphinoferrocene, 1-ferroceneacrylonitrile, 1-ferrocenylethanol, 1,1′-bis(1-hydroxyethyl) ferrocene, 1,1′-diacetylferrocene, 1,1′-diaminoferrocene, 1,1′-dibenzoylferrocene, 1,1′-dibutylferrocene, 1,1′-diethylferrocene, 1,1′-dihexylferrocene, 1,1′-dimethylferrocene, 1,1′-divinylferrocene, 1,1′-ferrocenedicarboxaldehyde, 1,1′-ferrocenedicarboxamide, 1,1′-ferrocenedicarboxylic acid, 1,1′-ferrocenedimethanol, 1,1′-ferrocenylacetic acid, 1,1′-ferrocenylpropanoic acid, 1,1′-ferrocenylbutanoic acid, 1,1′-ferrocenylpentanoic acid, 1,2,3,4,5-pentamethylferrocene, 2-ferrocenylethanol, 3-ferrocenylpropanol, 3-ferrocenylpropanoic acid, 4-ferrocenylbutanoic acid, 5-ferrocenylpentanoic acid, acetylferrocene, a-(N,N-dimethylamino)ethylferrocene, aminoferrocene, ethyl ferrocene, ferrocenylacetic acid, ferrocenyl methanol, octyl ferrocene, ferrocenecarboxylic acid, ferrocene carboxamide, ferrocene carboxal-dehyde, propyl ferrocene, hexyl ferrocene, hydroxyethyl ferrocene, benzoyl ferrocene, butyl ferrocene, methyl ferrocene, vinyl ferrocene, and bis(pentamethylcyclopentadienyl) iron (II), and
(D) 0 to 35 wt. % of at least one additive,
wherein the at least one additive is selected from the group consisting of inorganic stabilizers differing from component (C), organic stabilizers, antiozonants, light stabilizers, UV stabilizers, UV absorbers, UV blockers, IR absorbers, NIR absorbers, antiblocking agents, nucleating agents, crystallization accelerators, crystallization retarders, chain-extending additives, conductivity additives, release agents, lubricants, dyes, marking agents, inorganic pigments, organic pigments, carbon black, graphite, carbon nanotubes, graphene, titanium dioxide, zinc sulfide, zinc oxide, barium carbonate, barium sulfate, photochromic agents, antistatic agents, mold release agents, optical brighteners, halogen-free flame retardants, metallic pigments, metal flakes, metal-coated particles, fibrous or needle-shaped fillers, and particulate fillers,
components (A) to (D) adding up to 100 wt. %.
2. The polyamide compound according to claim 1 ,
wherein the at least one partially crystalline, partially aromatic polyamide (A) has at least one of the following properties:
a relative viscosity (RV), measured according to EN ISO 307 (2007), of 1.45 to 2.10,
a heat of fusion, measured according to EN ISO 11357-3 (2013), of at least 25 J/g, and
a melting temperature, measured according to EN ISO 11357-3 (2013), of at least 255° C.
3. The polyamide compound according to claim 1 ,
wherein the at least one partially crystalline, partially aromatic polyamide (A) is formed from the monomers (a1) to (a2) and optionally (a3) and optionally (a4):
(a1) at least one diamine selected from the group consisting of 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, bis(4-amino-cyclohexyl) methane, bis(4-amino-3-methyl-cyclohexyl) methane, bis(4-amino-3,5-dimethyl-cyclohexyl) methane, bis(aminomethyl)cyclohexane, isophoronediamine, m-xylylenediamine, and p-xylylenediamine, and
(a2) at least one aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and
(a3) at least one dicarboxylic acid selected from the group consisting of 1,6-hexanedioic acid, 1,9-nonanedioic acid, 1,10-decanedioic acid, 1,12-dodecanedioic acid, 1,13-tridecanedioic acid, 1,14-tetradecanedioic acid, 1,15-pentadecandoic acid, 1,16-hexadecanedioic acid, 1,17-heptadecanedioic acid, 1,18-octadecanedioic acid, cyclohexanedicarboxylic acid, and dimeric fatty acid having 36 or 44 C atoms, and
(a4) one or more lactams or ω-amino acids selected from the group consisting of lactam-6, lactam-11, lactam-12, 1,6-aminohexanoic acid, 1,11-aminoundecanoic acid, and 1,12-aminododecanoic acid.
4. The polyamide compound according to claim 1 ,
wherein the at least one partially crystalline, partially aromatic polyamide (A) is selected from the group consisting of PA 4T/66, PA 4T/6T, PA 4T/8T, PA 6T/8T, PA 4T/MPMDT, PA 4T/6T/MPMDT, PA 4T/4I, PA 4T/6I, PA 5T/5I, PA 6T/MPMDT, PA 6T/MPMDT/6I, PA 6T/6I, PA 6T/66, PA 6T/6, PA 6T/12, PA 6T/66/6, PA 6T/610, PA 6T/612, PA 6T/10I, PA 6T/9T, PA 6T/12T, PA 6T/6I/6, PA 6T/6I/66, PA 6T/6I/612, PA 6T/6I/12, PA 9T/MODT, PA 9T/91, PA 10T, PA 12T, PA 12T/12I, PA 10T/1012, PA 10T/6T, PA 10T/10I, PA10T/106, PA10T/12, PA10T/11, PA 10T/6T/612, PA 10T/6T/101/6I, PA 10T/6T/1012/612, PA 6T/BACT, PA 6T/BACT/66, PA 6T/6I/BACT/BACI, PA 6T/BACT/MACMT, PA 6T/BACT/PACMT, PA 6T/BACT/TMDCT, PA 4T/6T/8T, PA 4T/6T/10T, PA 4T/8T/10T, and PA 6T/8T/10T.
5. The polyamide compound according to claim 1 , wherein the at least one partially crystalline, partially aromatic polyamide (A) is free of lactams and ω-amino acids.
6. The polyamide compound according to claim 1 , wherein the partially crystalline, partially aromatic polyamide (A) is PA 6T/66, formed from:
50 mol % 1,6-hexanediamine,
14 to 40 mol % terephthalic acid, and
10 to 36 mol % 1,6-hexanoic acid;
wherein the 14 to 40 mol % terephthalic acid and the 10 to 36 mol % 1,6-hexanoic acid add up to 50 mol %.
7. The polyamide compound according to claim 1 , wherein
the at least one impact modifier (B) is (ii) a functionalized polymer formed by grafting a polymer selected from the group consisting of polyethylene, polypropylene, and a polyolefin copolymer, with a compound selected from the group consisting of an unsaturated carboxylic acid, unsaturated carboxylic acid derivative, and unsaturated glycidyl compound.
8. The polyamide compound according to claim 1 , wherein the at least one substituted metallocene has a melting temperature of 120° C. to 350° C.
9. The polyamide compound according to claim 1 , wherein the at least one substituted metallocene is substituted bis(η 5 -cyclopentadienyl)iron.
10. The polyamide compound according to claim 1 , wherein at least one particulate filler is selected from the group consisting of dolomite, silicates, quartz, talc, mica, kaolin, perlite, silica, precipitated or pyrogenic silicas, diatomaceous earth, titanium dioxide, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, ground or precipitated calcium carbonate, zinc oxide, zinc sulfide, chalk, lime, limestone powder, slate powder, feldspar, barium carbonate, barium sulfate, synthetic phyllosilicates, natural phyllosilicates, permanent magnetic or magnetizable metals or alloys, glass flakes, glass spheres, hollow glass spheres, and hollow spherical silicate fillers.
11. The polyamide compound according to claim 1 , wherein the polyamide compound comprises from 43 to 89.6 wt. % of component (A), from 10 to 25 wt. % of component (B), from 0.03 to 2.0 wt. % of component (C), and from 0.1 to 30 wt. % of component (D).
12. A mold produced from a polyamide compound according to claim 1 .
13. The mold according to claim 12 , which is a component of an automobile.
14. The mold according to claim 12 , which is a component of an engine compartment, or of an electrical, electronics, mechanical engineering, power generation, or power supply component.
15. The mold according to claim 12 , which is a component of a cylinder head cover, an engine cover, a housing, a fastening element, a part of charge air cooler, charge air cooler flap, intake pipe, exhaust pipe, connector, gear, fan wheel, cooling water tank, housing or part of a heat exchanger, coolant cooler, thermostat, water pump, radiator, foil, fastening part, cable, housing and/or a part of an electrical/electronic device, housing, a part of fan heater, switch, distributor, relay, resistor, capacitor, coil, lamp, diode, LED, transistor, connector, controller, memory unit, or sensor.